CN103435811A - Zirconium-containing high-temperature-resistant hybrid resin and preparation method thereof - Google Patents
Zirconium-containing high-temperature-resistant hybrid resin and preparation method thereof Download PDFInfo
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- CN103435811A CN103435811A CN2013104043694A CN201310404369A CN103435811A CN 103435811 A CN103435811 A CN 103435811A CN 2013104043694 A CN2013104043694 A CN 2013104043694A CN 201310404369 A CN201310404369 A CN 201310404369A CN 103435811 A CN103435811 A CN 103435811A
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Abstract
The invention discloses zirconium-containing high-temperature-resistant hybrid resin and a preparation method thereof. The resin disclosed by the invention is prepared from phenylacetylene, trichloro ethylene, organic lithium and zirconium halide through two-step reaction under the protection of inert gas. The preparation method disclosed by the invention comprises the following two steps of: (1), under the protection of inert gas, reacting the mixture of trichloro ethylene and phenylacetylene with organic lithium to obtain acetenyl bilithium and phenyl acetylene lithium; and (2), under the protection of inert gas, reacting the mixture of acetenyl bilithium and phenyl acetylene lithium, generated in the step one, with zirconium halide, and post-processing to obtain the final product. According to the preparation method, the molecular weight, the crosslinking density and the zirconium content of a polymer are easily controlled by adjusting the molar ratio of phenyl acetylene lithium with single functional group to acetenyl bilithium with double functional groups, and thus the performances of the polymer are adjustable. The used raw materials are easy to obtain and the operation process is simple and feasible; the prepared polymer can be black low-viscosity liquid or sticky solid, is easily dissolved in various ordinary organic solvents; and the prepared polymer can be used as a high-temperature-resistant composite material, a ceramic precursor, a high-temperature-resistant coating and the like and has extremely wide application prospect in the high-end fields such as national defense, aviation and spaceflight.
Description
Technical field
The present invention relates to a kind of high temperature resistant hybrid resin containing zirconium, the organic-inorganic hybridized polymkeric substance that particularly main chain contains zirconium atom and ethynyl, its main chain is comprised of Zr-C and C ≡ C, and simple function group phenylacetylene base compound carries out end-blocking to polymkeric substance.Curing cross-linking reaction occurs and forms tridimensional network in ethynyl under light, heat or initiator effect, further under high temperature action, forms ceramic structure.
Background technology
A series of special propertys that the hybrid inorganic-organic polymkeric substance shows (as thermotolerance, Burning corrosion resistance), make it become one of most active field in polymer material science research.Especially, the application of the high-technology fields such as aerospace has proposed more lightweight, more high-strength, the better requirement of resistance toheat to material, makes it become the very strong driving force that promotes the development of hybrid inorganic-organic polymkeric substance.Introduce resistant to elevated temperatures transition metal in polymkeric substance, form a kind of novel hybrid inorganic-organic materials, this hybrid material, aspect high temperature resistant, anti-ablation, having excellent performance, has now become the study hotspot of Chinese scholars.
Zirconium has surprising corrosion resistance, high fusing point, and its fusing point is more than 1800 ℃, and the fusing point of zirconium dioxide is especially up to more than 2700 ℃.So introduce zirconium in polymkeric substance, make this base polymer there is very excellent thermotolerance and Burning corrosion resistance energy.The method of introducing at present zirconium in polymkeric substance mainly contains doping method, chemical deposition and sol-gel method.Yet synthesize the method for introducing zirconium by precursor, research both domestic and external rarely has report.
(the Chemical Propellants& such as the king Yu Gang of HeFei University of Technology; Polymeric Materials, 2009,7(4): 37-39) by zirconium compounds, the form with the 3rd monomer is incorporated in the skeleton structure of resol, has obtained the zirconium resol that thermotolerance and carbon yield all are better than common resol.This resin has resistance toheat preferably, approximately 560 ℃ of maximum heat decomposition temperatures, and the carbon residue rate after 800 ℃ of lower charings is 62.5%, can be used as the resin matrix of good high temperature resistant and ablation resistant material.
The present invention has synthesized a kind of high temperature resistant hybrid resin containing zirconium.The repeating unit of resin structure is comprised of zirconium-ethynyl, by the phenylacetylene base end-blocking.Only contain carbon, hydrogen, three kinds of elements of zirconium in this polymkeric substance, higher containing the zirconium amount, this makes it have more excellent high temperature resistant and Burning corrosion resistance energy.Cross-linking and curing reaction occurs and forms tridimensional network in described polymkeric substance under the effect of light, heat or chemical initiator.Under high temperature action, further form ceramic structure, it has extremely broad application prospect in the high-end fields such as national defence, Aeronautics and Astronautics.
Summary of the invention
An object of the present invention is to provide a kind of novel high temperature resistant hybrid resin containing zirconium, this resin structure formula is as follows:
Wherein: the integer that n is >=1.
The invention provides a kind of brand-new polymer architecture, its repeating unit at least contains a zirconium-ethynyl structure, and containing two phenylacetylene base end-blockings.Phenylacetylene base lithium by regulating simple function group and the mol ratio of the ethynyl pair lithiums of bifunctional, control at an easy rate the content of molecular weight, cross-linking density and the zirconium of polymkeric substance, thereby reach the purpose of polymer performance adjustable.
Polymkeric substance of the present invention is extremely thick solid of black low-viscosity (mobile) liquid, is soluble in all kinds of ordinary organic solvents, can be used for preparing high temperature resistant composite, ceramic forerunner, high-temperaure coating.Cross-linking and curing reaction, under the effect of heat, light or chemical initiator, occurs in the ethynyl in polymkeric substance, forms the thermosetting material of tridimensional network.The further pyrolysis in air or rare gas element of this cured article can form ceramic structure.
Another object of the present invention is to provide a kind of method prepared containing the high temperature resistant hybrid resin of zirconium.The present invention be take trieline, phenylacetylene, organolithium and zirconium halide as raw material, take tetrahydrofuran (THF) as solvent, reacts in two steps under protection of inert gas and obtains, and the preparation method is as follows:
The first step: under protection of inert gas, the mixture of trieline and phenylacetylene is reacted with organolithium and obtain the two lithiums of ethynyl and phenylacetylene base lithium.
Wherein: R is alkyl or aryl, and R preferentially is chosen as butyl.
The invention is characterized in: the mol ratio of trieline and organolithium is 1:(3～4); The mol ratio of phenylacetylene and organolithium is 1:(1～2); The mol ratio of zirconium halide and trieline is 1:(1～3); Trieline and phenylacetylene mixture and organolithium temperature of reaction are-50 ℃～20 ℃, and the reaction times is 1～6 hour.
Second step: under protection of inert gas, the two lithiums of the ethynyl that the first step is generated and phenylacetylene lithium mixture and zirconium halide react, and aftertreatment obtains final product.
Wherein: X represents a kind of of F, Cl, Br or I, the integer that n is >=1.
The invention is characterized in: in the two lithiums of the acetylene that the first step reaction generates and phenylacetylene lithium mixture, the mol ratio of lithium and zirconium halide is (1～4): 1; The temperature of reaction of the two lithiums of ethynyl and phenylacetylene lithium mixture and zirconium halide is at-5 ℃～25 ℃, and the reaction times is 1～24 hour.
Synthesis technique of the present invention is simple, easy to operate.Required starting material source is abundant, and product at room temperature has satisfactory stability, and high temperature resistant and Burning corrosion resistance can be excellent, has industrial applicibility.
specific embodiments:
Technical scheme of the present invention is: under protection of inert gas, trieline and phenylacetylene are added drop-wise in organolithium successively, in-50 ℃～20 ℃, react 1～6 hour after dropwising.Then zirconium halide is added in the two lithiums of ethynyl and phenylacetylene base lithium solution, temperature of reaction, at-5 ℃～25 ℃, is reacted 1～24 hour.Reaction after finishing is removed solvent in product, then adds 50ml toluene to wash and suction filtration, gets filtrate and its underpressure distillation is removed to desolventizing, obtains final product.
The present invention has following advantage: technical process is simple, and operating procedure is simple, and reaction conditions is easy to control, and purifies without complicated aftertreatment, suitable extension production.The prepared high temperature resistant hybrid resin containing zirconium of the present invention can be applicable to prepare the multiple uses such as high performance composite, ceramic forerunner, high-temperaure coating.
embodiment:
Further illustrate technical solution of the present invention, but it does not limit the scope of the invention in conjunction with the embodiments.
Embodiment 1
First the butyllithium reagent of 75mmol is added in there-necked flask, again the phenylacetylene of the trieline of 22.5mmol and 7.5mmol is dissolved in the 30ml tetrahydrofuran (THF), with constant pressure funnel, splash in butyllithium reagent, time for adding 30min, dropwise in-20 ℃ of reactions 2 hours.Then be dissolved in the 15ml tetrahydrofuran (THF) by the zirconium tetrachloride of 13.13mmol and be added in the two lithiums of ethynyl and phenylacetylene base pair lithium mixtures, under 20 ℃, reaction is 24 hours.Reaction after finishing is removed solvent in product, then adds 50ml toluene to wash and suction filtration, gets filtrate and its underpressure distillation is removed to desolventizing, finally obtains black thickness resin, and productive rate is 37.8%.FT-IR(cm
-1):?2157(C≡C),?522(Zr–C),3062(Ph-H);H-NMR(CDCl
3,TMS,δ):?7.0-7.5?(Ph-H)。Its cured article is in nitrogen atmosphere, and 800 ℃ of quality retention rates are 30.7%; In air atmosphere, after 1000 ℃ of ablations, the quality retention rate is 15.0%, and zirconium content is 11.1%.
Embodiment 2
First the butyllithium reagent of 75mmol is added in there-necked flask, again the phenylacetylene of the trieline of 18.75mmol and 18.75mmol is dissolved in the 30ml tetrahydrofuran (THF), with constant pressure funnel, splash in butyllithium reagent, time for adding 30min, dropwise in-20 ℃ of reactions 2 hours.Then be dissolved in the 15ml tetrahydrofuran (THF) by the zirconium tetrachloride of 14.06mmol and be added in the two lithiums of ethynyl and phenylacetylene base pair lithium mixtures, under 20 ℃, reaction is 24 hours.Reaction after finishing is removed solvent in product, then adds 50ml toluene to wash and suction filtration, gets filtrate and its underpressure distillation is removed to desolventizing, finally obtains black thickness resin, and productive rate is 40.5%.FT-IR(cm
-1)：2160?(C≡C),?524(Zr–C),3055(Ph-H)；H-NMR
(CDCl
3,TMS,δ):7.1-7.5(Ph-H)。Its cured article is in nitrogen atmosphere, and 800 ℃ of quality retention rates are 37.8%; In air atmosphere, after 1000 ℃ of ablations, the quality retention rate is 26.5%, and zirconium content is 19.6%.
Claims (7)
1. the high temperature resistant hybrid resin containing zirconium is characterized in that described high temperature resistant hybrid resin has following structural formula:
Wherein: the integer that n is >=1.
2. the preparation method of the high temperature resistant hybrid resin containing zirconium claimed in claim 1, its key step is:
(1) the first step reaction: under protection of inert gas, the mixture of trieline and phenylacetylene is reacted with organolithium and obtain the two lithiums of ethynyl and phenylacetylene base lithium;
(2) second step reaction: under protection of inert gas, the two lithiums of the ethynyl that the first step is generated and phenylacetylene lithium mixture and zirconium halide react, and aftertreatment obtains final product.
3. preparation method according to claim 2, it is characterized in that: the mol ratio of trieline and organolithium is 1:(3～4); The mol ratio of phenylacetylene and organolithium is 1:(1～2); The mol ratio of zirconium halide and trieline is 1:(1～3).
4. preparation method according to claim 2 is characterized in that: in the first step reaction, trieline and phenylacetylene mixture and organolithium temperature of reaction are-50 ℃～20 ℃, and the reaction times is 1～6 hour.
5. preparation method according to claim 2 is characterized in that: in the two lithiums of the acetylene that the first step reaction generates and phenylacetylene lithium mixture, lithium is (1～4) with the mol ratio of zirconium halide: 1.
6. preparation method according to claim 2 is characterized in that: in the second step reaction, the temperature of reaction of the two lithiums of ethynyl and phenylacetylene lithium mixture and zirconium halide is-5 ℃～25 ℃, 1～24 hour reaction times.
7. preparation method according to claim 2, it is characterized in that: organolithium reagent is lithium alkylide or lithium aryl, preferentially is chosen as butyllithium.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119537A (en) * | 2014-07-21 | 2014-10-29 | 华东理工大学 | Zirconium-containing high-temperature-resistant resin and preparation method thereof |
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2013
- 2013-09-09 CN CN2013104043694A patent/CN103435811A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 张跃峰 等: "锆炔杂化树脂的制备及性能", 《功能高分子学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119537A (en) * | 2014-07-21 | 2014-10-29 | 华东理工大学 | Zirconium-containing high-temperature-resistant resin and preparation method thereof |
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Application publication date: 20131211 |